Diethyl (cyanomethyl)phosphonate → 3-(4-Biphenylyl)-3-(3,4-dimethoxyphenyl)acrylonitrile
Reaction equation
COC1C=C(C(C2C=CC(OC)=C(OC)C=2)=CC(OC)=O)C=CC=1OC.[CH3:27][O:28][C:29]1[CH:30]=[C:31]([CH:46]=[CH:47][C:48]=1[O:49][CH3:50])[C:32]([C:34]1[CH:39]=[CH:38][C:37]([C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)=[CH:36][CH:35]=1)=O.C(OP([CH2:59][C:60]#[N:61])(=O)OCC)C.C[Si](C)(C)[N-][Si](C)(C)C.[Li+]>>[C:37]1([C:40]2[CH:45]=[CH:44][CH:43]=[CH:42][CH:41]=2)[CH:38]=[CH:39][C:34]([C:32]([C:31]2[CH:46]=[CH:47][C:48]([O:49][CH3:50])=[C:29]([O:28][CH3:27])[CH:30]=2)=[CH:59][C:60]#[N:61])=[CH:35][CH:36]=1Participants
Procedure
3-(4-Biphenylyl)-3-(3,4-dimethoxyphenyl)acrylonitrile was prepared analogously to methyl 3,3-bis-(3',4'-dimethoxyphenyl)acrylate using 3,4-dimethoxy-4'-phenylbenzophenone (2.33 g, 7.32 mmol), diethylcyanomethylphosphonate (1.5 mL, 8.1 mmol) and lithium hexamethyldisilazide (8.1 mL, 8.1 mmol, 1M) with a reaction time of 22 hours. The crude product was purified by chromatography (silica gel, 1% ethyl acetate/methylene chloride) to afford 1.76 g (70%) of a mixture of the E and Z isomers as a white solid: mp 132.0-134° C.; 1H NMR (CDCl3) δ 7.70-7.39 (m, 18 H), 7.10-6.80 (m, 6 H), 5.69 (s, 1 H), 5.68 (s, 1 H), 3.95 (s, 6 H), 3.93 (s, 3 H), 3.89 (s, 3 H), 3.85 (s, 3 H); 13C NMR (CDCl3) δ 162.2, 151.1, 148.8, 148.6, 143.0, 142.6, 140.0, 137.9, 135.9, 131.4, 130.1, 129.3, 129.1, 128.8, 128.8, 127.9, 127.1, 127.0, 126.0, 126.9, 123.1, 122.2, 118.3, 118.2, 112.6, 111.1, 110.7, 93.2, 92.9, 56.0, 55.9, 55.8; Anal. Calcd for C23H19NO2. Theoretical: C, 80.92; H, 5.61; N, 4.10. Found: C, 80.55; H, 5.80; N, 3.95.
Workup
- customwith a reaction time of 22 hours
- customThe crude product was purified by chromatography (silica gel, 1% ethyl acetate/methylene chloride)
Sources & evidence
- ORD record
- ord-34d713da101d477b8e44b04a376aa38d
- Source dataset
- uspto-grants-2000_10
- Patent number
- US06130226
Reaction notes
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